Naphthindazole-4,9-quinones

ABSTRACT

Naphthindazole-4,9-quinones of the formula ##STR1## where R 1  to R 5  have the meanings given in the disclosure, and their use for combating unwanted plant growth.

This is a division of application Ser. No. 407,318, filed Sep. 14, 1989, now U.S. Pat. No. 5,007,954.

The present invention relates to naphthindazole-4,9-quinones and use thereof for controlling undesirable plant growth.

It has already been disclosed that indazolequinone derivatives have herbicidal properties (DE-A-2,107,053). Furthermore, naphthindazole-4,9-quinones are known from Chem. Ber. 97 (1964), 2555, and from Liebigs Ann. Chem. (1985), 251, but nothing is said about their use.

We have found that naphthindazole-4,9-quinones of the formula ##STR2## where R¹ is hydrogen, C₁ -C₁₀ -alkyl, C₂ -C₁₀ -alkenyl, C₂ -C₁₀ -alkynyl, C₁ -C₁₀ -haloalkyl, C₁ -C₁₀ -hydroxyalkyl, C₂ -C₁₄ -alkoxyalkyl, C₂ -C₁₄ -alkylthioalkyl, C₃ -C₇ -cycloalkyl, C₁ -C₄ -alkylcarbonyloxy-C₁ -C₄ -alkyl, C₁ -C₄ -alkylaminocarbonyloxy-C₁ -C₄ -alkyl, unsubstituted or halogen-, C₁ -C₄ -alkyl- or C₁ -C₄ -alkoxy-substituted (in the phenyl) phenylaminocarbonyloxy-C₁ -C₄ -alkyl, unsubstituted or halogen-, C₁ -C₄ -alkyl- or C₁ -C₄ -alkoxy-substituted (in the phenyl) phenylsulfonyloxy-C₁ -C₄ -alkyl, C₁ -C₄ -alkoxycarbonyl-C₁ -C₄ -alkyl, hydroxycarbonyl-C₁ -C₄ -alkyl, aminocarbonyl-C₁ -C₄ -alkyl, C₁ -C₄ -alkylaminocarbonyl-C₁ -C₄ -alkyl, di(C₁ -C₄ -alkyl)aminocarbonyl-C₁ -C₄ -alkyl, halogen-C₃ -C₄ -alkynyl, unsubstituted or halogen- or C₁ -C₄ -alkyl-substituted heteroaryl of one or two nitrogen atoms, unsubstituted or halogen-, hydroxyl-, nitro-, amino-, C₁ -C₄ -alkylamino-, di-C₁ -C₄ -alkylamino-, cyano-, C₁ -C₄ -alkyl-, C₁ -C₄ -alkoxy-, C₁ -C₄ -haloalkoxy-, C₁ -C₄ -haloalkyl-, C₁ -C₄ -alkylthio- or C₁ -C₄ -haloalkylthio-substituted phenyl or unsubstituted or halogen-substituted benzyl and

R², R³, R⁴ and R⁵ are each independently of the other hydrogen, halogen, nitro, cyano, hydroxyl, amino, C₁ -C₄ -alkylamino, di-C₁ -C₄ -alkylamino, C₁ -C₆ -alkyl, C₁ -C₅ -haloalkyl, C₁ -C₅ -alkoxy, C₁ -C₅ -haloalkoxy, C₁ -C₅ -alkylthio, C₁ -C₅ -haloalkylthio, C₂ -C₁₀ -alkoxyalkyl, carboxyl, C₂ -C₆ -alkoxycarbonyl, C₂ -C₆ -alkanoyloxy, C₂ -C₆ -haloalkanoyloxy, C₁ -C₄ -alkylcarbonylamino, C₁ -C₄ -alkylaminocarbonyl, di(C₁ -C₄ -alkyl)aminocarbonyl, or unsubstituted or halogen-, trifluoromethyl-, nitro-, cyano-, amino-, C₁ -C₄ -alkoxy-, C₁ -C₄ -alkylthio- or C₁ -C₅ -haloalkylthio-substituted phenyl or heteroaryl and in addition R³ and R⁴ together with the two carbon atoms of the phenyl ring to which they are bonded form a heterocyclic ring or an unsubstituted or halogen-, nitro-, cyano-, amino-, hydroxyl-, trifluoromethyl-, C₁ -C₅ -alkyl-, C₁ -C₅ -alkoxy-, C₁ -C₅ -haloalkylthio-, C₁ -C₅ -haloalkoxy- or C₁ -C₅ -alkylthiosubstituted benzene or naphthalene ring, have good herbicidal properties and are selectively active with respect to crop plants.

In the formula Ia, the radicals R¹, R², R³, R⁴ and R⁵ have the following meanings:

R¹ : hydrogen, C₁ -C₁₀ -alkyl, preferably C₁ -C₄ -alkyl, C₂ -C₁₀ -alkenyl, preferably C₂ -C₄ -alkenyl, C₂ -C₁₀ -alkynyl, preferably C₂ -C₄ -alkynyl, C₁ -C₁₀ -hydroxyalkyl, preferably C₁ -C₄ -hydroxyalkyl, C₂ -C₁₄ -alkoxyalkyl, preferably C₂ -C₆ -alkoxyalkyl, C₂ -C₁₄ -alkylthioalkyl, preferably C₂ -C₆ -alkylthioalkyl, C₃ -C₇ -cycloalkyl, preferably C₃ -C₆ -cycloalkyl, C₁ -C₄ -alkylcarbonyloxy-C₁ -C₄ -alkyl, C₁ -C₄ -alkylaminocarbonyloxy-C₁ -C₄ -alkyl, unsubstituted or halogen-, C₁ -C₄ -alkyl- or C₁ -C₄ -alkoxy-substituted (in the phenyl) phenylaminocarbonyloxy-C₁ -C₄ -alkyl, unsubstituted or halogen-, C₁ -C₄ -alkyl- or C₁ -C₄ -alkoxy-substituted (in the phenyl) phenylsulfonyloxy-C₁ -C₄ -alkyl, C₁ -C₄ -alkoxycarbonyl-C₁ -C₄ -alkyl, hydroxycarbonyl-C₁ -C₄ -alkyl, aminocarbonyl-C₁ -C₄ -alkyl, C₁ -C₄ -alkylaminocarbonyl-C₁ -C₄ -alkyl,di(C₁ -C₄ -alkyl)aminocarbonyl-C₁ -C₄ -alkyl, halo-C₃ -C₄ -alkynyl, unsubstituted or halogen- or C₁ -C₄ -alkyl-substituted heteroaryl of one or two nitrogen atoms, e.g. pyrimidyl, pyridyl or imidazolyl, unsubstituted or halogen-, hydroxyl-, nitro-, amino-, C₁ -C₄ -alkylamino-, di-C₁ -C₄ -alkylamino-, cyano-, C₁ -C₄ -alkyl-, C₁ -C₄ -haloalkyl-, C₁ -C₄ -alkoxy-, C₁ -C₄ -haloalkoxy-, C₁ -C₄ -alkylthio- or C₁ -C₄ -haloalkylthio-monosubstituted or polysubstituted phenyl, unsubstituted or halogen-monosubstituted or -poly-substituted (in the phenyl) benzyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, ter.-butyl, n-pentyl, tert.amyl, n-hexyl, pentyl-3, 1,2-dimethyl-n-propyl, 1,3-dimethyl-n-butyl, 1-ethyl-2-methyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1,2-dimethyl-4-hexyl, allyl, methallyl, crotyl, 2-ethylhex-2-enyl, hex-5-enyl, 2-methylbut-2-enyl, 2-methylbut-3-enyl, but-1-en-3-yl, 2-methylbut-1-en-4-yl, 2-methylbut-2-en-4-yl, 3-methylbut-1-en-3-yl, propargyl, but-1-yn-3-yl, but-2-ynyl, 2-chloroethyl, 2-chloro-n-propyl, 3-chloro-n-propyl, 2-chloro-sec.-butyl, 2-chloroisobutyl, 2-fluoro-sec.-butyl, 2-fluoroisobutyl, 2-fluoroisopropyl, chloro-tert.-butyl, 2,2,2-trifluoroethyl, hydroxymethyl, 2-hydroxyethyl, 3-hydroxy-n-propyl, 2-hydroxyisopropyl, 2-hydroxy-n-butyl, 3-hydroxy-n-butyl, 4-hydroxy-n-butyl, 2-hydroxyisobutyl, 2-methoxyethyl, 2-ethoxyethyl, 3-methoxy-n-propyl, 2-methoxyisopropyl, 3-methoxy-n-butyl, 1-methoxy-sec.-butyl, methoxy-tert.-butyl, ethoxy-tert.-butyl, 2-methoxy-n-butyl, 4-methoxy-n-butyl, cyclopropyl, cyclopentyl, cyclohexyl, 2-methylmercaptoethyl, 2-ethylmercaptoethyl, 3-methylmercapto-n-propyl, 3-methylmercapto-n-butyl, 1-methylmercapto-sec.-butyl, methylmercapto-tert.-butyl, 2-methylmercapto-n-butyl, phenyl, 4-chlorophenyl, 3,4-dichlorophenyl, o-, m- or p-tert-butylphenyl, o-, m- or p-methoxyphenyl, o-, m- or p-methylphenyl, 4-methoxy-3-chlorophenyl, 2-methyl-4-chlorophenyl, benzyl, 2,6-dichlorobenzyl, 2-chloro-6-fluorobenzyl, 2,6-difluorobenzyl or o-, m- or p-chlorobenzyl.

R², R³, R⁴, R⁵ : hydrogen, halogen, such as fluorine, chlorine, bromine or iodine, nitro, cyano, hydroxyl, amino, C₁ -C₄ -alkylamino, di-C₁ -C₄ -alkylamino, C₁ -C₆ -alkyl, preferably C₁ -C₄ -alkyl, C₁ -C₅ -haloalkyl, preferably C₁ -C₃ -haloalkyl, C₁ -C₅ -alkoxy, preferably C₁ -C₃ -alkoxy, C₁ -C₅ -haloalkoxy, preferably C₁ -C₃ -haloalkoxy, C₁ -C₅ -alkylthio, preferably C₁ -C₃ -alkylthio, C₁ -C₅ -haloalkylthio, preferably C₁ -C₃ -haloalkylthio, C₂ -C₁₀ -alkoxyalkyl, preferably C₂ -C₆ -alkoxyalkyl, carboxyl, C₂ -C₅ -alkoxycarbonyl, preferably C₂ -C₄ -alkoxycarbonyl, C₂ -C₆ -alkanoyloxy, preferably C₂ -C₄ -alkanoyloxy, C₃ -C₆ -haloalkanoyloxy, preferably C₂ -C₄ -haloalkanoyloxy, C₁ -C₄ -alkylcarbonylamino, C₁ -C₄ -alkylaminocarbonyl, di(C₁ -C₄ -alkyl)-aminocarbonyl, unsubstituted or halogen-, preferably chlorine- or fluorine-, trifluoromethyl-, nitro-, cyano-, amino-, C₁ -C₄ -alkoxy-, C₁ -C₄ -alkylthio- or C₁ -C₅ -haloalkylthio-substituted phenyl or heteroaryl, preferably pyridyl, pyrimidyl, thienyl, furyl or benzimidazolyl, e.g. methylamino, dimethylamino, ethylamino, diethylamino, isopropylamino, diisopropylamino, methylethylamino, n-, iso- or tert.-butylamino, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, tert.-butyl, n-pentyl, tert.-amyl, n-hexyl, pentyl-3, 1,2-dimethyl-n-propyl, 1,3-dimethyl-n-butyl, 1-ethyl-2-methyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1,2-dimethyl-n-hexyl, allyl, methallyl, crotyl, 2-ethylhex-2-enyl, hex-5-enyl, 2-methylbut-2-enyl, 2-methylbut-3-enyl, but-1-en-3-yl, 2-methylbut-1-en-4-yl, 2-methylbut-2-en-4-yl, 3-methylbut-1-en-3-yl, propargyl, but-1-yn-3-yl, but-2-ynyl, fluoromethyl, chloromethyl, trifluoromethyl, difluoromethyl, trichloromethyl, dichloromethyl, 2-chloroethyl, 2-chloro-n-propyl, 3-chloro-n-propyl, 2-chloroisopropyl, pentafluoroethyl, 2,2,2-trifluoroethyl, 2-fluoroisopropyl, 3-fluoro-n-propyl, 2-fluoroethyl, methoxy, ethoxy, n- or isopropoxy, n-, iso- or tert.-butoxy, pentoxy, difluoromethoxy, trifluoromethoxy, trichloromethoxy, methylthio, ethylthio, n- or isopropylthio, n-, iso- or tert.-butylthio, difluoromethylthio, trifluoromethylthio, methoxymethyl, ethoxymethyl, 2-methoxyethyl, 3-methoxy-n-propyl, 2-methoxyisopropyl, 2-ethoxyethyl, 3-ethoxy-n-propyl, 2-ethoxyisopropyl, methoxycarbonyl, ethoxycarbonyl, n- or isopropoxycarbonyl, n-, iso- or tert.-butoxycarbony, 2-methoxyethoxycarbonyl, ethoxymethoxycarbonyl, 2-ethoxyethoxycarbonyl, phenyl, o-, m- or p-fluorophenyl, o-, m- or p-chlorophenyl, 2,4-difluorophenyl, 2,4-p-trifluoromethylphenyl, 2-, 3-and 4-nitrophenyl, 2-, 3- and 4-cyanophenyl, 2-, 3-and 4-aminophenyl, 2-, 3- and 4-methoxyphenyl,2,4-dimethoxyphenyl,2,4,5-trimethoxyphenyl, 2-, 3- and 4-thiomethylphenyl, heteroaryl such as pyrid-2-yl, pyrid-3-yl, pyrid-4-yl, thien-2-yl, thien-3-yl, fur-2-yl, fur-3-yl, benzimidazol-2-yl, 3-chloropyrid-6-yl, 2-methylfur-5-yl, 2-methylthien-5-yl and 4,6-dimethylpyrimid-2-yl, acetyl, propionyl, butyryl, isobutyryl, valeroyl, isovaleroyl, pivaloyl, chloroacetyl, dichloroacetyl, trichloroacetyl, fluoroacetyl, difluoroacetyl, trifluoroacetyl, 3,3,3-trifluoropropionyl, pentafluoropropionyl, 2-chloropropionyl, 2,2-dichloropropionyl, 2-fluoropropionyl or 2,2-difluoropropionyl.

R³ and R⁴ may also form together with the two carbon atoms of the phenyl ring to which they are bonded an unsubstituted or fluorine-, chlorine-, bromine-, nitro-, cyano-, amino-, hydroxyl-, trifluoromethyl-, C₁ -C₅ -alkyl-, preferably C₁ -C₃ -alkyl-, C₁ -C₅ -alkoxy-, C₁ -C₅ -haloalkylthio-, C₁ -C₅ -haloalkoxy- or C₁ -C₅ -alkylthio-, preferably C₁ -C₃ -alkylthio-, substituted benzene or naphthalene ring.

Examples of heterocyclic rings formed by R³ and R⁴ together with the two carbon atoms of the phenyl ring to which they are bonded are 1,4-dioxane, 1,3-dioxolane, pyrazole, indole, thiophene, triazole and piperazine. Examples of the corresponding substituted rings are 2,2-dimethyl-1,3-dioxalane, 1-methylpyrazole, 1-methylindole,N,N'-dimethylpiperazine,2,2-diphenyl-1,3-dioxolane, and 2-oxo-1,3-dioxolane.

Naphthindazole-4,9-quinones of the formula Ia where R¹ is C₁ -C₄ -alkyl or C₂ -C₄ -alkenyl are preferred. Preference is further given to those compounds of the formula Ia where the substituents R² to R⁵ are each independently of the others hydrogen, hydroxyl, halogen, nitro, cyano, amino, C₁ -C₄ -alkylamino or di-C₁ -C₄ -alkylamino. Preference is given in particular to compounds where R² to R⁵ are each hydrogen, hydroxyl or halogen.

The naphthindazole-4,9-quinones of the formula ##STR3## where R¹, R², R³, R⁴ and R⁵ are each as defined for the formula Ia, with the proviso that R¹ is not hydrogen or methyl, are novel.

The naphthindazole-4,9-quinones of the formula I are obtained by reacting the 5-arylmethylpyrazol-4-yl carbonyl halides of the formula ##STR4## where R¹, R², R³, R⁴ and R⁵ are each as defined above and Hal is halogen, in an inert solubilizer in the presence of a Friedel-Crafts catalyst, and converting the resulting compounds of the formula ##STR5## where R¹, R², R³, R⁴ and R⁵ are each as defined above, in the presence of a diluent with oxidizing agents into the naphthindazole-4,9-quinones of the formula I.

Suitable inert solubilizers for this purpose are carbon disulfide, nitromethane, nitrobenzene, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, sulfolane, trichloroethylene and 1,1,1-trichloroethane.

Suitable Friedel-Crafts catalysts are aluminum trichloride, boron trifluoride, tin tetrachloride, titanium tetrachloride, zinc chloride, boron trichloride, trifluoroacetic acid, sulfuric acid, aluminum bromide, gallium chloride, iron(III) chloride, antimony pentachloride, antimony trichloride and zirconium tetrachloride. The amount of catalyst is from 5 to 500, preferably from 100 to 250, mol %, based on starting acid chloride of the formula II.

The reaction advantageously takes place at from 0° to 150° C.

The oxidation of compounds III is advantageously carried out in an inert diluent, such as acetic acid or alcoholic alkali metal hydroxide solution, in the presence or absence of water, at from 0° to 120° C. Suitable oxidizing agents are hydrogen peroxide and chromium(IV) oxide.

The oxidation is advantageously carried out by dissolving the starting compounds III in dilute, aqueous-alcoholic solutions of alkali metal hydroxides at temperatures of from 0° C. to 120° C., preferably from 50° C. to 100° C., and adding excess aqueous hydrogen peroxide solution. The reaction will in general have ended after 4-8, but not more than 24, hours. The solid end product is filtered off with suction and may be recrystallized or chromatographed for purification.

The synthesis of the 5-arylmethylpyrazol-4-yl carbonyl halides II can be effected in a conventional manner in accordance with the following scheme: ##STR6## (Y. Oikana, K. Sugano and O. Yonemitsu, J. Org. Chem. 43 (1978), 2087) ##STR7## (G. Menozzi, L. Mosti and P. Schenone, J. Heterocycl. Chem. 24 (1987), 1969) ##STR8##

The naphthindazole-4,9-quinones of the formula I are likewise obtained on reacting substituted 1,4-naphthoquinones of the formula ##STR9## where R², R³, R⁴ and R⁵ are each as defined above, with diazomethane in the presence of inert diluents, for example aliphatic or alicyclic ethers, oxidizing the resulting compounds of the formula ##STR10## where R², R³, R⁴ and R⁵ are each as defined above, in an inert diluent and alkylating the resulting naphthindazole-4,9-quinones of the formula ##STR11## where R², R³, R⁴ and R⁵ are each as defined above, with an alkylating agent of the formula

    R.sup.1 --X                                                (VII)

where

R¹ is as defined above and

X is p-toluenesulfonate, mesylate, brosylate, halogen or a group of the formula ##STR12## where R¹ is as defined above, in a diluent in the presence of a base at from -30° C. to +100° C.

The reaction of the 1,4-naphthoquinones IV with diazomethane can be carried out in a conventional manner (Houben-Weyl, Methoden der org. Chemie, volume 7/3a, page 553 (1977)). The oxidation of compounds V is possible inter alia with hydrogen peroxide, chromium(VI) oxide or atmospheric oxygen in an inert diluent, such as dilute acetic acid or methyl t-butyl ether.

The alkylation of the naphthindazole-4,9-quinones VI with the alkylating agent VII takes place in a conventional manner in a diluent, for example water or acetone or mixtures thereof, in the presence of a base, such as alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal carbonates or alkali metal or alkaline earth metal bicarbonates. It is preferable to work at from 10° to 30° C.

All the other starting compounds and reaction products whose preparation has not been described in detail are either known or can be prepared by known principles.

PREPARATION EXAMPLES EXAMPLE 1 ##STR13##

A suspension of 20.6 g (0.13 mol) of 1,4-naphthoquinone in 500 ml of methyl t-butyl ether is admixed under a protective gas atmosphere at 0° C. with 400 ml of a 3.5×10⁻⁴ M solution (0.14 mol) of diazomethane in diethyl ether. After the addition has ended, the suspension is heated to room temperature, and air is passed through the reaction mixture overnight. The precipitate formed is then filtered off with suction, washed with 100 ml of methyl t-butyl ether and stirred into 75 ml of hot ethanol. It is filtered off with suction, washed with 100 ml of ethanol and dried. Yield: 12.1 g (47% of theory). Melting point: 180° C. decomposition.

Example 2 ##STR14##

6.0 g (0.03 mol) of naphthindazole-4,9-quinone (Example 1) are suspended in 100 ml of 80% strength aqueous acetone and admixed at room temperature in succession with 3.2 g (0.03 mol) of sodium carbonate and 7.3 g (0.06 mol) of 1-bromo-2-propene. The mixture is stirred overnight and then refluxed for three hours. It is cooled down, admixed with a further 1.1 g (0.01 mol) of sodium carbonate and 2.4 g (0.02 mol) of 1-bromo-2-propene and refluxed for a further two hours. It is then concentrated under reduced pressure and extracted four times with 100 ml of dichloromethane each time. The combined extracts are dried over sodium sulfate and concentrated. The crystalline residue is chromatographed over silica gel (mobile phase: cyclohexane/ethyl acetate) to obtain 4.6 g (64% of theory) of 1-(propen-2-yl)naphthindazole-4,9-quinone of melting point 105°-108° C.

Example 3 ##STR15##

a) 1.25 g (0.005 mol) of 5-(4-chlorophenylmethyl)-1-methylpyrazol-4-yl carboxylic acid (preparation: G. Menozzi, L. Mosti and P. Schenone, J. Heterocycl. Chem. 24 (1987), 1669) are dissolved in 2 ml of thionyl chloride and refluxed for one hour. Excess thionyl chloride is then removed under reduced pressure (12 mmHg), the residue is taken up in 20 ml of diethyl ether, and the mixture is stirred with 2.0 g of active charcoal. The mixture is filtered after 30 minutes, the filtrate is concentrated under reduced pressure to give 1.25 g (93% of theory) of acid chloride as a colorless oil.

b) 1.25 g (4.6 mmol) of 5-(4-chlorophenylmethyl)-1-methylpyrazol-4-yl carbonyl chloride are dissolved in 5 ml of nitromethane and added to a 0° C. solution of 1.85 g (14 mmol) of aluminum chloride in 20 ml of nitromethane. The mixture is stirred at room temperature overnight and then poured into a mixture of 50 g of ice and 20 ml of concentrated hydrochloric acid. The organic phase is separated off, the aqueous phase is extracted twice more with 50 ml of dichloromethane each time and the combined extracts are dried over sodium sulfate. Removing the solvent under reduced pressure leaves 1.10 g (100% of theory) of 6-chloro-9-hydro-1-methylnaphthindazol-4-one of melting point>270° C. ¹ H-NMR (250 MHz, DMSO-d₆): 4.05 (s; 3H), 4.45 (s; 2H), 7.35 (dd, J=9.2 and 0.2 Hz; 1H), 7.90 (d,J= 9.0 Hz; 1H), 8.20 (d, J=0.2 Hz; 1H), 8.45 (s; 1H)

c) 1.10 g (4.6 mmol) of 6-chloro-9-hydro-1-methyl-naphthindazol-4-one are dissolved in a mixture of 10 ml of 10% strength sodium hydroxide solution and 50 ml of methanol by heating (80° C.). The solution is cooled down to 60° C., and 5 ml of a 30% strength solution of hydrogen peroxide are added. The mixture is stirred at room temperature overnight, and the precipitated quinone is then filtered off with suction, giving 0.85 g (57% of theory) of 1-methyl-6-chloronaphthindazol-4,9-quinone of melting point 219° C. ¹ H-NMR (250 MHz, CDCl₃): 4.35 (s; 3H), 7.72 (d, J=9.0 Hz; 1H), 8.05 (s; 1H), 8.18 (s; 1H), 8.18 (d, J=9.0 Hz; 1H).

The following compounds of the formulae I and Ia can be obtained in a similar manner:

    __________________________________________________________________________     Ex. no.                                                                               R.sup.1            R.sup.2 -R.sup.5           Melting point                                                                  [°C.]              __________________________________________________________________________      4     CH.sub.3           H                          181                        5     CH.sub.2 CH.sub.3  H                          151-152                    6     isopropyl          H                          126                        7     n-propyl           H                                                     8     n-butyl            H                           69                        9     t-butyl            H                          152                        10    2-pentyl           H                          164                        11    cyclopentyl        H                                                     12    cyclohexyl         H                          148                        13    CH.sub.2CF.sub.3   H                          171                        14    CH.sub.2OH         H                                                     15    CH.sub.2CH.sub.2OH H                          158                        16                                                                                    ##STR16##         H                          109                        17                                                                                    ##STR17##         H                          116                        18                                                                                    ##STR18##         H                          179                        19                                                                                    ##STR19##         H                          155                        20    CH.sub.2COOC.sub.2 H.sub.5                                                                        H                          149                        21    CH.sub.2 COOH      H                                                     22                                                                                    ##STR20##         H                                                     23                                                                                    ##STR21##         H                                                     24                                                                                    ##STR22##         H                                                     25    CH.sub.2 CH.sub.2SCH.sub.3                                                                        H                                                     26    CH.sub.2SCH.sub.3  H                                                     27    CH.sub.2CCH        H                          193                        28    CH.sub.2CCBr       H                                                     29    phenyl             H                          221                        30    benzyl             H                          154                        31    2-(4,6-dimethylpyrimidinyl)                                                                       H                          237                        32    2-pyridinyl        H                          221                        33    2-(2-imidazoline)  H                                                     34    2,4-dichlorophenyl H                                                     35    2,4,6-trichlorophenyl                                                                             H                                                     36    4-fluorophenyl     H                                                     37    2,4-difluorophenyl H                                                     38    2,4,6-trifluorophenyl                                                                             H                                                     39    4-methoxyphenyl    H                                                     40    2,4-dimethoxyphenyl                                                                               H                                                     41    4-thiomethylphenyl H                                                     42    4-trifluoromethylphenyl                                                                           H                                                    __________________________________________________________________________     Example no.                                                                           R.sup.1            R.sup.2 R.sup.3                                                                             R.sup.4                                                                             R.sup.5  Melting point                                                                  [°C.]              __________________________________________________________________________      43    CH.sub.3           F       H    H    H        195                        44    CH.sub.3           H       F    H    H                                   45    CH.sub.3           H       H    F    H        173                        46    CH.sub.3           H       H    H    F                                   47    CH.sub.3           Cl      H    H    H                                   48    CH.sub.3           H       Cl   H    H        219                        49    CH.sub.3           H       H    Cl   H        226                        50    CH.sub.3           H       H    H    Cl                                  51    CH.sub.3           Br      H    H    H                                   52    CH.sub.3           H       H    H    Br       190-192                    53    CH.sub.3           Cl      H    H    Cl                                  54    CH.sub.3           H       Cl   H    Cl       230                        55    CH.sub.3           H       Cl   Cl   H                                   56    CH.sub.3           F       H    H    F                                   57    CH.sub.3           H       F    H    F                                   58    CH.sub.3           H       F    F    H                                   59    CH.sub.3           OH      H    H    H        190                        60    CH.sub.3           H       OH   H    H                                   61    CH.sub.3           H       H    OH   H                                   62    CH.sub.3           H       H    H    OH       212                        63    CH.sub.3           OH      H    H    OH       224-227                    64    CH.sub.3           OCH.sub.3                                                                              H    H    H                                   65    CH.sub.3           H       OCH.sub.3                                                                           H    H        193                        66    CH.sub.3           H       H    OCH.sub.3                                                                           H        173                        67    CH.sub.3           H       H    H    OCH.sub.3                                                                               230                        68    CH.sub.3           OCH.sub.3                                                                              H    CH.sub.3                                                                            H        212-213                    69    CH.sub.3           OH      H    H    OCH.sub.3                           70    CH.sub.3           OCH.sub.3                                                                              H    H    OH                                  71    CH.sub.3           OCH.sub.3                                                                              OCH.sub.3                                                                           H    OCH.sub.3                           72    CH.sub.3           OH      OCH.sub.3                                                                           H    OCH.sub.3                           73    CH.sub.3           OCH.sub.3                                                                              H    OCH.sub.3                                                                           H        212                        74    CH.sub.3           OCH.sub.3                                                                              H    OCH.sub.3                                                                           OH                                  75    CH.sub.3           OH      H    OCH.sub.3                                                                           H        208                        76    CH.sub.3           H       OCH.sub.3                                                                           H    OCH.sub.3                           77    CH.sub.3           H       OCH.sub.3                                                                           H    OH                                  78    CH.sub.3           H       OCH.sub.2CH.sub.2 O                                                                      H                                   79    CH.sub.3           H       OCH.sub.2O                                                                               H        252                        80    CH.sub.3           H       OH   OH   H                                   81    CH.sub.3           SCH.sub.3                                                                              H    H    H                                   82    CH.sub.3           H       SCH.sub.3                                                                           H    H                                   83    CH.sub.3           H       H    SCH.sub.3                                                                           H                                   84    CH.sub.3           H       H    H    SCH.sub.3                           85    CH.sub.3                                                                                           ##STR23##                                                                             H    H    H        220                        86    CH.sub.3           H       H    H                                                                                    ##STR24##                          87    CH.sub.3           CH.sub.3                                                                               H    H    H                                   88    CH.sub.3           H       CH.sub.3                                                                            H    H        177                        89    CH.sub.3           H       H    CH.sub.3                                                                            H        136                        90    CH.sub.3           H       H    H    CH.sub.3 218                        91    CH.sub.3           CH.sub.3                                                                               H    H    CH.sub.3 143                        92    CH.sub.3           CF.sub.3                                                                               H    H    H                                   93    CH.sub.3           H       CF.sub.3                                                                            H    H                                   94    CH.sub.3           H       H    CF.sub.3                                                                            H                                   95    CH.sub.3           H       H    H    CF.sub.3                            97    CH.sub.3           H       CH.sub.3                                                                            H    OH       154                        97    CH.sub.3           OH      H    CH.sub.3                                                                            H        175                        98    CH.sub.3           H       C.sub.4 H.sub.4                                                                          OH       288                        99    CH.sub.3           H       C.sub.4 H.sub.4                                                                          H                                  100    CH.sub.3           OH      C.sub.4 H.sub.4                                                                          H                                  101    CH.sub.3           H       C.sub.4 H.sub.4                                                                           ##STR25##                                                                              253                       102    CH.sub.3                                                                                           ##STR26##                                                                             C.sub.4 H.sub.4                                                                          H        231                       103    CH.sub.3           F       C.sub.4 H.sub.4                                                                          OH                                 104    CH.sub.3           NO.sub.2                                                                               H    H    H                                  105    CH.sub.3           H       H    H    NO.sub.2                           106    CH.sub.3           NH.sub.2                                                                               H    H    H                                  107    CH.sub.3           H       H    H    NH.sub.2                           108    CH.sub.3                                                                                           ##STR27##                                                                             H    H    H                                  109    CH.sub.3           H       H    H                                                                                    ##STR28##                         110    CH.sub.3           CN      H    H    H                                  111    CH.sub.3           H       CN   H                                       112    CH.sub.3           H       H    H    CN                                 113    CH.sub.3           C.sub.6 H.sub.5                                                                        H    H    H                                  114    CH.sub.3           H       C.sub.6 H.sub.5                                                                     H    H        185                       115    CH.sub.3           H       H    C.sub.6 H.sub.5                                                                     H                                  116    CH.sub.3           H       H    H    C.sub.6 H.sub.5                    117    CH.sub.3           COOCH.sub.3                                                                            H    H    H                                  118    CH.sub.3           H       H    H    COOCH.sub.3                        119    CH.sub.3           COOH    H    H    H                                  120    CH.sub.3           H       H    H    COOH                               121    CH.sub.3           CONHCH.sub.3                                                                           H    H    H                                  122    CH.sub.3           H       H    H    CONHCH.sub.3                       123    CH.sub.3           CON(CH.sub.3 ).sub.2                                                                   H    H    H                                  124    CH.sub.3           H       H    H    CON(CH.sub.3).sub.2                125    C.sub.6 H.sub.5    OH      H    H    OH       208                       126    C.sub.6 H.sub.5    OH      H    H    H                                  127    C.sub.6 H.sub.5    H       H    H    OH                                 128    C.sub.6 H.sub.5    F       H    H    H                                  129    C.sub.6 H.sub.5    H       H    F    H                                  130    C.sub.6 H.sub.5    H       H    H    F                                  131    C.sub.6 H.sub.5    Cl      H    H    H                                  132    C.sub.6 H.sub.5    H       H    H    Cl                                 133    C.sub.6 H.sub.5    OH      H    OCH.sub.3                                                                           H                                  134    C.sub.6 H.sub.5    OCH.sub.3                                                                              H    OH   H                                  135    C.sub.6 H.sub.5    H       OCH.sub.3                                                                           H    OH                                 136    C.sub.6 H.sub.5    CF.sub.3                                                                               H    H    H                                  137    C.sub.6 H.sub.5    H       H    CF.sub.3                                                                            H                                  138    C.sub.6 H.sub.5    H       H    H    CF.sub.3                           139    C.sub.6 H5         NH.sub.2                                                                               H    H    H                                  140    C.sub.6 H5         H       H    NH.sub.2                                                                            H                                  141    C.sub.6 H5         H       H    H    NH.sub.2                           142    C.sub.6 H5         H       NO.sub.2                                                                            H    H                                  143    C.sub.6 H5         NO.sub.2                                                                               H    H    H                                  144    C.sub.6 H5         F       F    H    H                                  145    isopropyl          H       CF.sub.3                                                                            H    H                                  146    isopropyl          H       H    CF.sub.3                                                                            H                                  147    isopropyl          H       H    H    CF.sub.3                           148    isopropyl          H       CH.sub.3                                                                            H    OH                                 149    isopropyl          OH      H    CH.sub.3                                                                            H                                  150    isopropyl          H       C.sub.4 H.sub.4                                                                          OH                                 151    isopropyl          H       C.sub.4 H.sub.4                                                                          H                                  152    isopropyl          OH      C.sub.4 H.sub.4                                                                          H                                  153    isopropyl          H       C.sub.4 H.sub.4                                                                           ##STR29##                         154    isopropyl                                                                                          ##STR30##                                                                             C.sub.4 H.sub.4                                                                          H                                  155    isopropyl          F       C.sub.4 H.sub.4                                                                          OH                                 156    isopropyl          NO.sub.2                                                                               H    H    H                                  157    isopropyl          H       H    H    NO.sub.2                           158    isopropyl          NH.sub.2                                                                               H    H    H                                  159    isopropyl          H       H    H    NH.sub.2                           160    isopropyl                                                                                          ##STR31##                                                                             H    H    H                                  161    isopropyl          H       H    H    NHCOCH.sub.3                       162    isopropyl          CN      H    H    H                                  163    isopropyl          H       CN   H    H                                  164    isopropyl          H       H    H    CN                                 165    isopropyl          C.sub.6 H.sub.5                                                                        H    H    H                                  166    isopropyl          H       C.sub.6 H.sub.5                                                                     H    H                                  167    isopropyl          H       H    C.sub.6 H.sub.5                                                                     H                                  168    isopropyl          H       H    H    C.sub.6 H.sub.5                    169    isopropyl          COOCH.sub.3                                                                            H    H    H                                  170    isopropyl          H       H    H    COOCH.sub.3                        171    isopropyl          F       H    H    H                                  172    isopropyl          H       F    H    H                                  173    isopropyl          H       H    F    H                                  174    isopropyl          H       H    H    F                                  175    isopropyl          Cl      H    H    H                                  176    isopropyl          H       Cl   H    H                                  177    isopropyl          H       H    Cl   H                                  178    isopropyl          H       H    H    Cl                                 179    isopropyl          Br      H    H    H                                  180    isopropyl          F       H    H    Br                                 181    isopropyl          Cl      H    H    Cl                                 182    isopropyl          H       Cl   H    Cl                                 183    isopropyl          H       Cl   Cl   H                                  184    isopropyl          F       H    H    F                                  185    isopropyl          H       F    H    F                                  186    isopropyl          H       F    F    H                                  187    isopropyl          OH      H    H    H                                  188    isopropyl          H       OH   H    H                                  189    isopropyl          H       H    OH   H                                  190    isopropyl          H       H    H    OH                                 191    isopropyl          OH      H    H    OH                                 192    isopropyl          OCH.sub.3                                                                              H    H    H                                  193    isopropyl          H       OCH.sub.3                                                                           H    H        176                       194    isopropyl          H       H    OCH.sub.3                                                                           H        160                       195    isopropyl          H       H    H    OCH.sub.3                          196    isopropyl          OCH.sub.3                                                                              H    H    OCH.sub.3                          197    isopropyl          OH      H    H    OCH.sub.3                          198    isopropyl          OCH.sub.3                                                                              H    H    OH                                 199    isopropyl          OCH.sub.3                                                                              OCH.sub.3                                                                           H    OCH.sub.3                          200    isopropyl          OH      OCH.sub.3                                                                           H    OCH.sub.3                          201    isopropyl          OCH.sub.3                                                                              H    OCH.sub.3                                                                           OCH.sub.3                          202    isopropyl          OCH.sub.3                                                                              H    OCH.sub.3                                                                           OH                                 203    isopropyl          OH      H    OCH.sub.3                                                                           H                                  204    isopropyl          H       OCH.sub.3                                                                           H    OCH.sub.3                          205    isopropyl          H       OCH.sub.3                                                                           H    OH                                 206    isopropyl          H       OCH.sub.2CH.sub.2 O                                                                      H                                  207    isopropyl          H       OCH.sub.2O                                                                               H                                  208    isopropyl          H       OH   OH   H                                  209    isopropyl          SCH.sub.3                                                                              H    H    H                                  210    isopropyl          H       SCH.sub.3                                                                           H    H                                  211    isopropyl          H       H    SCH.sub.3                                                                           H                                  212    isopropyl          H       H    H    SCH.sub.3                          213    isopropyl                                                                                          ##STR32##                                                                             H    H    H                                  214    isopropyl          H       H    H                                                                                    ##STR33##                         215    isopropyl          CH.sub.3                                                                               H    H    H                                  216    isopropyl          H       CH.sub.3                                                                            H    H                                  217    isopropyl          H       H    CH.sub.3                                                                            H                                  218    isopropyl          H       H    H    CH.sub.3                           219    isopropyl          CH.sub.3                                                                               H    H    CH.sub.3                           220    isopropyl          CF.sub.3                                                                               H    H    H                                  221    isopropyl          COOH    H    H    H                                  222    isopropyl          H       H    H    COOH                               223    isopropyl          CONHCH.sub.3                                                                           H    H    H                                  224    isopropyl          H       H    H    CONHCH.sub.3                       225    isopropyl          CON(CH.sub.3).sub.2                                                                    H    H    H                                  226    isopropyl          H       H    H    CON(CH.sub.3).sub.2                227    CH.sub.2CCH        OH      H    H    H                                  228    CH.sub.2CCH        H       H    H    OH                                 229    CH.sub.2CCH        OCH.sub.3                                                                              H    H    H                                  230    CH.sub.2CCH        H       H    H    OCH.sub.3                          231    CH.sub.2CCH        OH      H    OCH.sub.3                                                                           H                                  232    CH.sub.2CCH        H       OCH.sub.3                                                                           H    OH                                 233    CH.sub.2CCH        F       H    H    H                                  234    CH.sub.2CCH        H       H    F    H                                  235    CH.sub.2CCH        H       H    H    F                                  236    CH.sub.2CCH        Cl      H    H    H                                  237    CH.sub.2CCH        H       H    H    Cl                                 238    CH.sub.2CCH        H       H    H    Br                                 239    CH.sub.2CCH        CF.sub.3                                                                               H    H    H                                  240    CH.sub.2CCH        H       H    CF.sub.3                                                                            H                                  241    CH.sub.2CCH        H       H    H    CF.sub.3                           242    CH.sub.2CCH        H       OCH.sub.3                                                                           H    H                                  243    CH.sub.2CCH        H       H    OCH.sub.3                                                                           H                                  244    CH.sub.2CCH        CN      H    H    H                                  245    CH.sub.2CCH        H       H    CN   H                                  246    CH.sub.2CCH        H       H    H    CN                                 247    allyl              F       H    H    H                                  248    allyl              H       F    H    H                                  249    allyl              H       H    F    H                                  250    allyl              H       H    H    F                                  251    allyl              Cl      H    H    H                                  252    allyl              H       Cl   H    H                                  253    allyl              H       H    Cl   H                                  254    allyl              H       H    H    Cl                                 255    allyl              Br      H    H    H                                  256    allyl              H       H    H    Br                                 257    allyl              Cl      H    H    Cl                                 258    allyl              H       Cl   H    Cl                                 259    allyl              H       Cl   Cl   H                                  260    allyl              F       H    H    F                                  261    allyl              H       F    H    F                                  262    allyl              H       F    F    H                                  263    allyl              OH      H    H    H                                  264    allyl              H       OH   H    H                                  265    allyl              H       H    OH   H                                  266    allyl              H       H    H    OH                                 267    allyl              OH      H    H    OH                                 268    allyl              OCH.sub.3                                                                              H    H    H                                  269    allyl              H       OCH.sub.3                                                                           H    H                                  270    allyl              H       H    OCH.sub.3                                                                           H                                  271    allyl              H       H    H    H                                  272    allyl              OCH.sub.3                                                                              H    H    OCH.sub.3                          273    allyl              OH      H    H    OCH.sub.3                          274    allyl              OCH.sub.3                                                                              H    H    OH                                 275    allyl              OCH.sub. 3                                                                             OCH.sub.3                                                                           H    OCH.sub.3                          276    allyl              OH      OCH.sub.3                                                                           H    OCH.sub.3                          277    allyl              OCH.sub.3                                                                              H    OCH.sub.3                                                                           OCH.sub.3                          278    allyl              OCH.sub.3                                                                              H    OCH.sub.3                                                                           OH                                 279    allyl              OH      H    OCH.sub.3                                                                           H                                  280    allyl              H       OCH.sub.3                                                                           H    OCH.sub.3                          281    allyl              H       OCH.sub.3                                                                           H    OH                                 282    allyl              H       OCH.sub.2CH.sub.2 O                                                                      H                                  283    allyl              H       OCH.sub.2O                                                                               H                                  284    allyl              H       OH   OH   H                                  285    allyl              SCH.sub.3                                                                              H    H    H                                  286    allyl              H       SCH.sub.3                                                                           H    H                                  287    allyl              H       H    SCH.sub.3                                                                           H                                  288    allyl              H       H    H    SCH.sub.3                          289    allyl                                                                                              ##STR34##                                                                             H    H    H                                  290    allyl              H       H    H                                                                                    ##STR35##                         291    allyl              CH.sub.3                                                                               H    H    H                                  292    allyl              H       CH.sub.3                                                                            H    H                                  293    allyl              H       H    CH.sub.3                                                                            H                                  294    allyl              H       H    H    H                                  295    allyl              CH.sub.3                                                                               H    H    CH.sub.3                           296    allyl              CF.sub.3                                                                               H    H    H                                  297    allyl              H       CF.sub.3                                                                            H    H                                  298    allyl              H       H    CF.sub.3                                                                            H                                  299    allyl              H       H    H    CF.sub.3                           300    allyl              H       CH.sub.3                                                                            H    OH                                 301    allyl              OH      H    CH.sub.3                                                                            H                                  302    allyl              H       C.sub.4 H.sub.4                                                                          OH                                 303    allyl              H       C.sub.4 H.sub.4                                                                          H                                  304    allyl              OH      C.sub.4 H.sub.4                                                                          H                                  305    allyl              H       C.sub.4 H.sub.4                                                                           ##STR36##                         306    allyl                                                                                              ##STR37##                                                                             C.sub.4 H.sub.4                                                                          H                                  307    allyl              F       C.sub.4 H.sub.4                                                                          OH                                 308    allyl              NO.sub.2                                                                               H    H    H                                  309    allyl              H       H    H    NO.sub.2                           310    allyl              NH.sub.2                                                                               H    H    H                                  311    allyl              H       H    H    NH.sub.2                           312    allyl                                                                                              ##STR38##                                                                             H    H    H                                  313    allyl              H       H    H                                                                                    ##STR39##                         314    allyl              CN      H    H    H                                  315    allyl              H       CN   H    H                                  316    allyl              H       H    H    CN                                 317    allyl              C.sub.6 H.sub.5                                                                        H    H    H                                  318    allyl              H       C.sub.6 H.sub.5                                                                     H    H                                  319    allyl              H       H    C.sub.6 H.sub.5                                                                     H                                  320    allyl              H       H    H    C.sub.6 H.sub.5                    321    allyl              COOCH.sub.3                                                                            H    H    H                                  322    allyl              H       H    H    COOCH.sub.3                        323    allyl              COOH    H    H    H                                  324    allyl              H       H    H    COOH                               325    allyl              CONHCH.sub.3                                                                           H    H    H                                  326    allyl              H       H    H    CONHCH.sub.3                       327    allyl              CON(CH.sub.3).sub.2                                                                    H    H    H                                  328    allyl              H       H    H    CON(CH.sub.3)2                     329    allyl              N(CH.sub.3).sub.2                                                                      H    H    H                                  330    allyl              H       H    H    N(CH.sub.3)2                       331    allyl              F       H    H    NH.sub.2                           332    allyl              NH.sub.2                                                                               H    H    F                                  __________________________________________________________________________

The active ingredients have a herbicidal action and are selective in crop plants.

The compounds, and herbicidal agents containing them, may be applied for instance in the form of directly sprayable solutions, powders, suspensions (including high-percentage aqueous, oily or other suspensions), dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of application depend entirely on the purpose for which the agents are being used, but they must ensure as fine a distribution of the active ingredients according to the invention as possible.

For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., and strongly polar solvents such as N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc. are suitable.

Aqueous formulations may be prepared from emulsion concentrates, pastes, oil dispersions or wettable powders by adding water. To prepare emulsions, pastes and oil dispersions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing agents, adherents or emulsifiers. Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent or oil.

Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, e.g., ligninsulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylaryl sulfonates, and alkyl, lauryl ether and fatty alcohol sulfates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, and salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and methyl cellulose.

Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.

Granules, e.g., coated, impregnated or homogeneous granules, may be prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silicic acid, silica gels, silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain meals, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.

The formulations contain from 0.1 to 95, and preferably 0.5 to 90, % by weight of active ingredient.

Examples of formulations are given below.

I. 90 parts by weight of compound no. 2 is mixed with 10 parts by weight of N-methyl-alpha-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.

II. 20 parts by weight of compound no. 4 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

III. 20 parts by weight of compound no. 6 is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide and 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

IV. 20 parts by weight of compound no. 59 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction having a boiling point between 210° and 280° C., and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

V. 20 parts by weight of compound no. 45 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-alpha-sulfonic acid, 17 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained containing 0.1% by weight of the active ingredient.

VI. 3 parts by weight of compound no. 4 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of the active ingredient.

VII. 30 parts by weight of compound no. 6 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.

VIII. 20 parts by weight of compound no. 59 is intimately mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.

The active ingredients or the herbicidal agents containing them may be applied pre- or postemergence. If certain crop plants tolerate the active ingredients less well, application techniques may be used in which the herbicidal agents are sprayed from suitable equipment in such a manner that the leaves of sensitive crop plants are if possible not touched, and the agents reach the soil or the unwanted plants growing beneath the crop plants (post-directed, lay-by treatment).

The application rates depend on the objective to be achieved, the time of the year, the plants to be combated and their growth stage, and are from 0.01 to 5.0, preferably 0.05 to 3.0, kg of active ingredient per hectare. The herbicidal action of the naphthindazoles of the formula I on the growth of test plants is illustrated by the following greenhouse experiments.

The vessels employed were plastic flowerpots having a volume of 300 cm³ and filled with a sandy loam containing about 3.0% humus. The seeds of the test plants were swon separately, according to species.

For the postemergence treatment, the plants were grown, depending on growth form, to a height of 3 to 15 cm before being treated. In this treatment method, either plants which had been sown in the pots and grown there were selected, or they were cultivated separately as seedlings and transplanted to the pots a few days before being treated with the compounds suspended or emulsified in water. The application rates for post-emergence treatment were 0.5 and 1.0 kg/ha.

The pots were set up in the greenhouse, species from warmer climates in warmer areas (20° to 35° C.) and species from moderate climates at 10° to 20° C. The experiments were run for from 2 to 4 weeks. During this time the plants were tended and their reactions to the various treatments assessed.

The assessment scale was 0 to 100, 100 denoting nonemergence or complete destruction of at least the visible plant parts, and 0 denoting no damage or normal growth.

The plants used in the greenhouse experiments were Amaranthus retroflexus, Ipomoea spp., Setaria italica, Solanum nigrum and Veronica spp.

The compounds of Examples 2, 4, 6, 45 and 59, applied postemergence at rates of 0.5 and 1.0 kg/ha, combated unwanted plants excellently.

In view of the number of application methods possible, the compounds according to the invention, or agents containing them, may be used in a further large number of crops for removing unwanted plants. The following crops are given by way of example:

    ______________________________________                                         Botanical name         Common name                                             ______________________________________                                         Allium cepa            onions                                                  Ananas comosus         pineapples                                              Arachis hypogaea       peanuts                                                                        (groundnuts)                                            Asparagus officinalis  asparagus                                               Avena sativa           oats                                                    Beta vulgaris spp. altissima                                                                          sugarbeets                                              Beta vulgaris spp. rapa                                                                               fodder beets                                            Beta vulgaris spp. esculenta                                                                          table beets,                                                                   red beets                                               Brassica napus var. napus                                                                             rapeseed                                                Brassica napus var. napobrassica                                                                      swedes                                                  Brassica napus var. rapa                                                                              turnips                                                 Brassica rapa var. silvestris                                                  Camellia sinensis      tea plants                                              Carthamus tinctorius   safflower                                               Carya illinoinensis    pecan trees                                             Citrus limon           lemons                                                  Citrus maxima          grapefruits                                             Citrus reticulata      mandarins                                               Citrus sinensis        orange trees                                            Coffea arabica (Coffea canephora,                                                                     coffee plants                                           Coffea liberica)                                                               Cucumis melo           melons                                                  Cucumis sativus        cucumbers                                               Cynodon dactylon       Bermudagrass                                            Daucus carota          carrots                                                 Elais guineensis       oil palms                                               Fragaria vesca         strawberries                                            Glycine max            soybeans                                                Gossypium hirsutum (Gossypium arboreum,                                                               cotton                                                  Gossypium herbaceum, Gossypium vitifolium)                                     Helianthus annuus      sunflowers                                              Helianthus tuberosus   Jerusalem artichoke                                     Hevea brasiliensis     rubber plants                                           Hordeum vulgare        barley                                                  Humulus lupulus        hops                                                     Ipomoea batatas       sweet potatoes                                          Juglans regia          walnut trees                                            Lactuca sativa         lettuce                                                 Lens culinaris         lentils                                                 Linum usitatissimum    flax                                                    Lycopersicon lycopersicum                                                                             tomatoes                                                Malus spp.             apple trees                                             Manihot esculenta      cassava                                                 Medicago sativa        alfalfa (lucerne)                                       Mentha piperita        peppermint                                              Musa spp.              banana plants                                           Nicotiana tabacum (N. rustica)                                                                        tobacco                                                 Olea europaea          olive trees                                             Oryza sativa           rice                                                    Panicum miliaceum      millet                                                  Phaseolus lunatus      limabeans                                               Phaseolus mungo        mungbeans                                               Phaseolus vulgaris     snapbeans,                                                                     green beans,                                                                   dry beans                                               Pennisetum glaucum     pearl millet                                            Petroselinum crispum spp. tuberosum                                                                   parsley                                                 Picea abies            Norway spruce                                           Abies alba             fir trees                                               Pinus spp.             pine trees                                              Pisum sativum          English peas                                            Prunus avium           cherry trees                                            Prunus domestica       plum trees                                              Prunus dulcis          almond trees                                            Prunus persica         peach trees                                             Pyrus communis         pear trees                                              Ribes sylvestre        redcurrants                                             Ribes uva-crispa       gooseberries                                            Ricinus communis       castor-oil plants                                       Saccharum officinarum  sugar cane                                              Secale cereale         rye                                                     Sesamum indicum        sesame                                                  Solanum tuberosum      Irish potatoes                                          Sorghum bicolor (s. vulgare)                                                                          sorghum                                                 Sorghum dochna         sorgo                                                   Spinacia oleracea      spinach                                                 Theobroma cacao        cacao plants                                             Trifolium pratense    red clover                                              Triticum aestivum      wheat                                                   Triticum durum         durum wheat                                             Vaccinium corymbosum   blueberries                                             Vaccinium vitis-idaea  cranberries                                             Vicia faba             tick beans                                              Vigna sinensis (V. unguiculata)                                                                       cow peas                                                Vitis vinifera         grapes                                                  Zea mays               Indian corn,                                                                   sweet corn, maize                                       ______________________________________                                    

To increase the spectrum of action and to achieve synergistic effects, the naphthindazoles of the formula I may be mixed and applied together with numerous representatives of other herbicidal or growth-regulating active ingredient groups. Examples of suitable components are diazines, 4H-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroanilines, N-phenylcarbamates, thiolcarbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, triazinones, uracils, benzofuran derivatives, cyclohexane-1,3-dione derivatives, quinolinecarboxylic acids, (het)aryloxyphenoxypropionic acids and salts, esters and amides thereof, etc.

It may also be useful to apply the novel compounds of the formula I, either alone or in combination with other herbicides, in admixture with other crop protection agents, e.g., agents for combating pests or phytopathogenic fungi or bacteria. The compounds may also be mixed with solutions of mineral salts used to remedy nutritional or trace element deficiencies. Non-phytotoxic oils and oil concentrates may also be added. 

We claim:
 1. A naphthindazole-4,9-quinone of the formula ##STR40## where: R¹ is C₃ -C₁₀ -alkenyl or C₂ -C₁₀ -alkynyl andR², R³, R⁴ and R⁵ are identical or different and each denotes hydrogen, halogen, nitro, cyano, hydroxy, amino, C₁ -C₄ -alkylamino, di-C₁ -C₄ -alkylamino, C₁ -C₆ -alkyl, C₁ -C₅ -haloalkyl, C₁ -C₅ -alkoxy, C₁ -C₅ -haloalkoxy, C₁ -C₅ -alkylthio, C₁ -C₅ -haloalkylthio, C₂ -C₁₀ -alkoxyalkyl, carboxyl, C₂ -C₆ -alkoxycarbonyl, C₂ -C₆ -alkanoyloxy, C₂ -C₆ -haloalkanoyloxy, C₁ -C₄ -alkylcarbonylamino, C₁ -C₄ -alkylaminocarbonyl, di-(C₁ -C₄ -alkyl)-aminocarbonyl, or phenyl or heteroaryl, each of which is unsubstituted or substituted by halogen, trifluoromethyl, nitro, cyano, amino, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio or C₁ -C₅ -haloalkylthio.
 2. The naphthindazole-4,9-quinone of claim 1, wherein R¹ is C₃ -C₄ -alkenyl.
 3. The naphthindazole-4,9-quinone of claim 1, wherein R² to R⁵ are identical or different and each denotes hydrogen, hydroxy or halogen.
 4. The naphthindazole-4,9-quinone of claim 1, wherein R¹ is 2-propenyl and R², R³, R⁴ and R⁵ are each hydrogen. 